JP2007262337A - Decorative sheet and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in adhesion to a polyolefin-based substrate, and a laminate using the same. <P>SOLUTION: This decorative sheet comprises a substrate film, a pattern layer and an adhesive layer containing a modified polyolefin, wherein the adhesive layer is formed by applying an aqueous dispersion or non-aqueous dispersion of the modified polyolefin to the substrate film and by drying the resultant coat. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a decorative sheet that is attached to the surface of a polyolefin-based molded body for the purpose of imparting designability or surface protection, and a laminate using the decorative sheet.

  Plastic molded products are excellent in mechanical properties, heat resistance, chemical resistance, and water resistance, and are therefore widely used in the field of industrial materials such as home appliances, building components and automobiles. Among them, various resins such as vinyl chloride, nylon, PET, polycarbonate, ABS, and polyolefin are widely used as general-purpose resins. However, it is considered that the range of use of polyolefins is further expanded in terms of suppressing emission of harmful substances and recyclability. However, in general, polyolefins such as polyethylene and polypropylene have a problem that they are low in polarity because they do not have a polar group in the molecule, and are difficult to paint or bond.

On the other hand, in recent years, in order to improve the design properties of these industrial materials, the appearance of various decorations such as woodgrain, fabric, and metal is often required, and decorative sheets and decorative sheets are made of plastic. There is an increasing demand for laminates laminated on molded bodies.
For example, Patent Document 1 discloses an adhesive layer made of a mixture of acrylic resin / vinyl chloride / vinyl acetate copolymer based on methyl (meth) acrylate and butyl (meth) acrylate copolymer as a decorative sheet, Decorated sheets have been proposed. However, the object is limited to an easily adhesive resin such as an ABS resin molded body, and adhesion to a molded body with low adhesion such as a polyolefin-based molded body has not been realized.

Patent Document 2 proposes a decorative transfer sheet using a polyolefin compound in which only the terminal is modified as an adhesive layer. Specifically, the adhesive layer is formed by applying and drying a solution of the compound in xylene. However, aromatic solvents such as xylene have a large environmental load due to volatilization of the solvent during drying, and it is a problem to form an adhesive layer without using such a solvent. Further, in the case of application by a solution, there is a problem that it is difficult to improve the adhesion to a polyolefin-based molded article because the molecular weight of the polyolefin that can be dissolved is limited to a relatively small one. In addition, since the solution viscosity tends to increase, there is a restriction that the dissolution concentration must be kept low, and a large amount of solvent must be used, and a thick adhesive layer is formed because it must be applied with a dilute solution There are issues that are difficult to do. Also, when you want to use a polar resin such as polyurethane or polyester to improve the adhesion and physical properties with the base material, the solution does not mix well when the polar resin is mixed with a highly hydrophobic solution such as a polyolefin compound. However, there is a problem that it is difficult to separate.
JP-A-8-276544 Japanese Patent Laid-Open No. 2001-262084

  In view of the above problems, an object of the present invention is to provide a decorative sheet having excellent adhesion to a polyolefin-based molded article, a laminate using the decorative sheet, and a method for producing the same.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a decorative sheet comprising an adhesive layer containing a base film, a pattern layer, and a modified polyolefin, and the adhesive layer is coated with an aqueous dispersion or a non-aqueous dispersion of the modified polyolefin and dried. The present invention relates to a decorative sheet that is formed.
In the present invention, the modified polyolefin is a block and / or graft copolymer of a polyolefin and a polar polymer, and the surfactant content is 15 parts by mass or less with respect to 100 parts by mass of the modified polyolefin. About.

The present invention also relates to a decorative sheet in which the base film is made of a radiation curable resin.
Furthermore, this invention relates to the laminated body characterized by the said decorative sheet being laminated | stacked on a polyolefin-type molded object.
Furthermore, the present invention is a method for producing a decorative sheet comprising a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, and after forming the pattern layer on the base film, an aqueous dispersion of the modified polyolefin or It is related with the manufacturing method of the decorating sheet | seat characterized by forming a contact bonding layer by apply | coating and drying a non-aqueous dispersion.

  Furthermore, the present invention is a method for producing a decorative sheet comprising a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, wherein an aqueous dispersion or non-aqueous dispersion of the modified polyolefin is applied on another base material. And then drying to form an adhesive layer, forming a pattern layer, applying and curing a radiation curable resin to form a base film, and then peeling the other base material. It relates to the manufacturing method.

  According to the present invention, since the adhesive layer of the decorative sheet is formed by applying an aqueous dispersion or non-aqueous dispersion of a modified polyolefin and drying it, it is possible to use a modified polyolefin having a large molecular weight compared to a solution. This has the advantage of easily improving the adhesion to the polyolefin-based molded product. Moreover, since the viscosity can be kept low even if a large amount of the modified polyolefin is dispersed by using a dispersion, a dispersion having a high modified polyolefin concentration can be used, and a thick adhesive layer can be easily formed. Further, by using a dispersion, there is an advantage that the modified polyolefin and the polar resin are not separated even when used in combination, and the adhesion to the substrate and the physical properties are easily improved. Furthermore, it is not necessary to use an aromatic solvent such as xylene, and VOC (volatile organic chemical substances) emission due to the volatilization of the solvent can be reduced. If an aqueous dispersion is used, the burden on the environment is even smaller.

  In addition, the modified polyolefin according to the present invention is very excellent in dispersibility in a polar solvent and water, and therefore has an advantage that the dispersed particle diameter is fine and the particle size distribution can be narrowed so that it can be stably dispersed. Moreover, since it can disperse | distribute without adding very little surfactant or substantially, there exists an advantage which can suppress the bleed-out by surfactant, and the coated article of the outstanding external appearance is obtained by extension. In addition, a dispersion having excellent properties can be obtained substantially without containing chlorine, and there are no problems such as dioxin and toxicity, which is very preferable in terms of environment.

Furthermore, the adhesive layer according to the present invention has high adhesion to both the base film and the polyolefin-based molded article, exhibits good adhesion to a molded article containing polyolefin or the like, and is usually untreated polypropylene that is difficult to bond. It is possible to adhere to a hardly adhesive molded body such as Moreover, it is excellent in water resistance, moisture resistance, oil resistance (GH resistance), and chemical resistance.
Moreover, the laminated body which laminated | stacked this decorating sheet on the polyolefin-type molded object is excellent in adhesiveness, and peeling is difficult to occur and it can apply to a wide industrial product. Therefore, polyolefin-based molded articles excellent in suppression of harmful substance emission and recyclability can be used even in fields where application of polyolefin-based molded articles has been difficult.

  In the present invention, it is not always essential to exhibit all the effects, and it is only necessary to have one or more of the effects described above.

The decorative sheet of the present invention is a decorative sheet comprising a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, and the adhesive layer is coated with an aqueous dispersion or non-aqueous dispersion of the modified polyolefin and dried. Formed.
The modified polyolefin (II) of the present invention is a non-chlorinated polyolefin which does not substantially contain chlorine, and is formed by bonding a polar polymer (IIB) or an acidic group to the polyolefin (IIA). It is the polymer (IIC) which becomes. That is, it is a polymer in which a polar polymer is bonded to a non-chlorinated polyolefin at a predetermined ratio or an acidic group is bonded. Such a polymer is very excellent in dispersibility in water and polar solvents, so by using a very small amount of surfactant without any surfactant, the dispersed particle size is fine, the particle size distribution is narrow, and the particles are stable. Dispersed aqueous dispersion and non-aqueous dispersion can be obtained.

A dispersion in which the modified polyolefin is dispersed in water is referred to as an aqueous dispersion, and a dispersion in which the modified polyolefin is dispersed in a solvent other than water, usually a polar solvent, is referred to as a non-aqueous dispersion.
In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved.
This will be described in more detail below.

[1] Polyolefin (IIA)
As the polyolefin (IIA), various known polyolefins can be used, and are not particularly limited. For example, a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, ethylene or / and propylene and other comonomers, For example, copolymers with α-olefin comonomers having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene and norbornene, or two types of these comonomers The above copolymers can be used.

  The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms. Copolymers of α-olefin monomers and comonomers such as vinyl acetate, acrylic acid esters and methacrylic acid esters, copolymers of comonomers such as aromatic vinyl monomers or hydrogenated products thereof, and conjugated diene block copolymers A hydrogenated product or the like can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer.

  Specific examples of polyolefin (IIA) include propylene polymer, propylene-ethylene copolymer, propylene-butene copolymer, styrene-butadiene-styrene triblock hydrogenated product (SEBS), styrene-isoprene- Styrene triblock hydrogenated product (SEPS). A propylene homopolymer, a propylene-ethylene copolymer, and a propylene-butene copolymer are preferable, and a propylene-butene copolymer is more preferable.

  The polyolefin (IIA) preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC (Gel Permeation Chromatography) and converted with a calibration curve of each polyolefin. A more preferable value of the lower limit value is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the lower limit, the degree of stickiness tends to decrease and the adhesion to the substrate tends to increase, and as the Mw is lower than the upper limit, the viscosity tends to decrease and the resin dispersion tends to be easily prepared. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

  The molecular weight distribution Mw / Mn represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the polyolefin (IIA) is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. This means that the molecular weight distribution is narrow and the molecular weight of the copolymer is uniform. By using such a copolymer (IIA), it is easy to control the particle size during dispersion in water. Thus, there is an advantage that a dispersed resin particle having a small dispersed particle size, a narrow particle size distribution, and a stable dispersion can be obtained. Preferably Mw / Mn is 3.0 or less. However, it is usually 1.0 or more.

  The polyolefin (IIA) preferably has a melting point Tm of 120 ° C. or lower. More preferably, it is 110 degrees C or less, More preferably, it is 100 degrees C or less. The melting point Tm lower than 120 ° C. is preferable because the crystallinity is low and the solubility in a solvent is improved, and the emulsification / dispersion work is easily performed at a low temperature. However, the melting point Tm of the polyolefin (IIA) is usually 25 ° C. or higher, preferably 35 ° C. or higher. It is free in terms of high heat resistance, high hardness and non-stickiness.

Preferably, the content of propylene in the polyolefin (IIA) is 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.
Polyolefin (IIA) may be used individually by 1 type, and may be used in combination of 2 or more type.

The production method of the polyolefin (IIA) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any production method may be used. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.
In the case of coordination polymerization, for example, a polymerization method using a Ziegler-Natta catalyst or a polymerization method using a single site catalyst or a Kaminsky catalyst can be used. A preferable production method includes a production method using a single site catalyst. The reason for this is that single-site catalysts are generally easy to control the reaction precisely due to the ligand design, yielding a polymer with a sharp molecular weight distribution and stereoregularity distribution, and have a melting point compared to polymers based on Ziegler-Natta catalysts. This is because the resin dispersion using this polymer can lower the baking temperature after coating because it is low. As the single site catalyst, for example, a metallocene catalyst or a Brookhart catalyst can be used. C ₁ symmetric type metallocene catalyst, C ₂ symmetric, C _2V symmetric, C _S symmetric like, it may be selected preferred catalyst in accordance with the stereoregularity of the polyolefin to be polymerized. Preferably, a C ₁ symmetric type or C ₂ symmetric type metallocene catalyst can be used.

  The polymerization may be any polymerization form such as solution polymerization, slurry polymerization, bulk polymerization, and gas phase polymerization. In the case of solution polymerization or slurry polymerization, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic carbonization such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrogen, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples include alcohols such as ethanol, n-propanol, isopropanol, and n-butanol; ethers such as dibutyl ether and tetrahydrofuran; and polar solvents such as dimethylformamide and dimethyl sulfoxide. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, hexane, heptane, cyclopentane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

[2] Polymer (IIC1) formed by bonding an acidic group to polyolefin (IIA)
The acidic group in the present invention refers to an electron pair accepting group, and is not particularly limited. For example, a carboxylic acid group (—COOH), a sulfo group (—SO ₃ H), a sulfino group (—SO ₂ H), and a phosphono group. _(-PO 2 H), and the like. Of these, a carboxyl group is preferred. The carboxylic acid group may be in a dicarboxylic anhydride group (—CO—O—OC—) before being dispersed in water. Examples of the carboxylic acid group include a (meth) acrylic acid group, a fumaric acid group, a maleic acid group or an anhydride group thereof, an itaconic acid group or an anhydride group thereof, and a crotonic acid group.

  The amount of acidic groups bonded is preferably in the range of 0.4 to 5 mmol, ie 0.4 to 5 mmol / g, per gram of polyolefin (IIA). A more preferred lower limit is 0.6 mmol / g, and a more preferred lower limit is 0.8 mmol / g. A more preferred upper limit is 3 mmol / g, and a more preferred upper limit is 1.6 mmol / g. The higher the lower limit value, the greater the polarity of the polymer (IIC1) and the more hydrophilic, the smaller the dispersed particle size. The lower the upper limit value, the higher the adhesion to the crystalline polyolefin as the substrate. . In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

  About the manufacturing method of polyolefin polymer (IIC1), the method similar to the manufacturing method of copolymer (IIA2) which a reactive group couple | bonds with polyolefin (IIA) mentioned later in [3-1] can be used.

[3] Polymer (IIC2) in which polar polymer (IIB) is bonded to polyolefin (IIA)
The ratio of polyolefin (IIA) to polar polymer (IIB) is usually (IIA) :( IIB) = 100: 5 to 100: 500 parts by weight. If the ratio of the polar polymer (IIB) is smaller than this range, the polymer (IIC2) does not disperse well in water, and the dispersed particle size is very large and aggregates or separates. On the other hand, if the ratio of the polar polymer (IIB) is larger than this range, the adhesion with the polyolefin-based molded article is deteriorated.

  As a method for producing a polymer (IIC2) by bonding a polyolefin (IIA) and a polar polymer (IIB), a polar high polymer bonded to the polyolefin (IIA) by polymerizing a polar monomer in the presence of the polyolefin (IIA) is usually used. Examples include a method (R1) for forming a molecule (IIB), or a method (R2) for bonding a prepolymerized polar polymer (IIB) to a polyolefin (IIA). The polyolefin (IIA) and polar polymer (IIB) What is necessary is just to select suitably according to a kind, a combination, the characteristic of the target polymer (IIC2), etc. Further, the polar polymer (IIB) may be directly bonded to the polyolefin (IIA), or the polymer (IIA2) in which a reactive group is bonded to the polyolefin (IIA) described below is used, and the polar polymer is used for this. (IIB) may be bound.

[3-1] Copolymer (IIA2) formed by bonding a reactive group to polyolefin (IIA)
As the polyolefin (IIA2) having a reactive group, for example, a copolymer (IIA2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization, or reactive A polymer (IIA2b) obtained by graft-polymerizing a radically polymerizable unsaturated compound having a group to a polyolefin (IIA), and a polymer obtained by converting a polyolefin copolymer having an unsaturated end group into a group 13 to 17 element group ( IIA2c) can be used.

  The copolymer (IIA2a) is obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is inserted into the main chain. Copolymer. For example, it can be obtained by copolymerizing an α-olefin such as ethylene, propylene or butene and an α, β-unsaturated carboxylic acid or anhydride such as acrylic acid or maleic anhydride. Specifically as a copolymer (IIA2a), a propylene-butene-maleic anhydride copolymer etc. can be used, for example. These may be used individually by 1 type and may be used in combination of 2 or more type. As the manufacturing method, the method described in [1] can be similarly used.

  The polymer (IIA2b) is obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin (IIA), and the unsaturated compound having a reactive group is grafted to the main chain. Yes. For example, polyolefins such as polyethylene and polypropylene, (meth) acrylic acid, fumaric acid, maleic acid or anhydride thereof, itaconic acid or anhydride thereof, crotonic acid, 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid It is a polymer grafted with 2-hydroxypropyl, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid (2-isocyanato) ethyl, or the like. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and others are based on this.

As polyolefin (IIA) of this reaction, the above-mentioned copolymer (IIA2a) can be used.
Specific examples of the polymer (IIA2b) include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified propylene-ethylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include a modified propylene-ethylene copolymer and its chlorinated product, and an acrylic acid-modified propylene-butene copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used for the graft polymerization can be appropriately selected from ordinary radical initiators, and examples thereof include organic peroxides and azonitriles. Examples of organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. Diacyl peroxides such as oxides and peroxyesters such as t-butylperoxyisopropyl monocarbonate can be used. Examples of the azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide and t-butylperoxyisopropyl monocarbonate are particularly preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

The use ratio of the radical polymerization initiator and the graft copolymer unit is usually in the range of radical polymerization initiator: graft copolymer unit = 1: 100 to 2: 1 (molar ratio). Preferably it is the range of 1: 20-1: 1.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 200 ° C. The reaction time is usually about 2 to 20 hours.

  The production method of the polymer (IIA2b) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any production method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. As a solvent in the case of producing in a solution, the solvents mentioned in [1] can be used similarly.

  As the polymer (IIA2c), for example, as described in JP-A-2001-288372, a double bond portion of a polyolefin (IIA) having a terminal double bond is a group 13 element such as a boron group or an aluminum group. Polyolefin (IIA2c1) converted into a group, polyolefin (IIA2c2) in which double bonds of a polyolefin having terminal double bonds are converted to halogen elements as described in JP-A-2005-48172, and JP-A-2001 2001 Polyolefin (IIA2c3) in which the double bond portion of a propylene-based polymer having a terminal double bond is converted to a mercapto group as described in No. -98140 can be used.

Examples of the method for producing a polyolefin having a double bond (IIA) include a method of causing α-hydrogen elimination during olefin polymerization and a method of thermally decomposing a propylene-based polymer at a high temperature.
Examples of a method for converting a double bond portion into a boron group or an aluminum group include a method in which an organic boron compound or an organic aluminum compound is reacted with a double bond in a solvent.

As a method for converting the double bond portion into a halogen element, for example, after converting the above-mentioned polyolefin having an organic boron group (IIA2c1) to a propylene-based polymer having a hydroxyl group by reacting a base and hydrogen peroxide solution, There is a method in which a halogen group-containing acid halide is reacted to convert it into a halogen group-containing ester group.
As a method for converting the double bond portion into a mercapto group, for example, there is a method in which thioacetic acid is reacted in the presence of a radical initiator and then treated with a base.

The production method of the polymer (IIA2c) is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any production method may be used, but a method of heating and stirring in a solution is preferably used. As a solvent in the case of producing in a solution, the solvents mentioned in [1] can be used similarly.
The content of reactive groups in the copolymers (IIA2a) and (IIA2b) obtained by bonding reactive groups should be in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g of polyolefin. Is preferred. A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, and particularly preferably 0.5 mmol / g.

  The content of the reactive group in the copolymer (IIA2c) obtained by bonding the reactive group is usually 1 reactive group or less per polymer molecule from the production method, and the 1 / number average molecular weight Mn (mol / g). It tends to be lower than those of the copolymers (IIA2a) and (IIA2b). Accordingly, it is preferably in the range of 0.004 to 2 mmol / g per gram of polyolefin. A more preferred lower limit is 0.005 mmol / g. A more preferred upper limit is 0.2 mmol / g.

  The higher the lower limit value is, the more the polar polymer (IIB) is bound and the hydrophilicity of the polymer (IIC) is increased, so the dispersed particle size tends to be smaller. There is a tendency for adhesion to polyolefin to increase. In addition, since it can be considered that a dicarboxylic acid anhydride group contains two carboxylic acid groups in a group, 1 mol of dicarboxylic acid anhydride groups is counted as 2 mol of reactive groups.

The copolymer (IIA2) may be linear or branched. As the copolymer (IIA2), one type may be used alone, or two or more types may be used in combination.
In the present invention, both the polyolefin (IIA) itself and the copolymer (IIA2) formed by bonding a reactive group are combined with the polar polymer (IIB), the characteristics of the target polymer (IIC), etc. Can be used as appropriate. However, it is preferable to include at least a copolymer (IIA2) formed by bonding a reactive group. There are advantages such as easy control of the binding amount of the polar polymer (IIB) and various reactions that can be used for binding. Only the copolymer (IIA2) formed by bonding a reactive group may be used.

Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, mercapto groups, and halogen groups. More preferably, it is at least one selected from the group consisting of a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group. These carboxylic acid groups are not only highly reactive and easy to bond with polar polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted onto polyolefins.
Although any of the polymers (IIA2a), (IIA2b), and (IIA2c) can be used, the polymer (IIA2b) is usually preferable. There are advantages such as easy control of the amount of binding of the polar polymer (IIB).

[3-2] Polar polymer (IIB)
In the following, only the copolymer (IIA) will be described for simplification of explanation, but the same applies to the copolymer (IIA2).
In the present invention, the polar polymer is a polymer having oxygen atoms and nitrogen atoms in addition to carbon atoms and hydrogen atoms in a repeating unit constituting the polymer, and a solubility parameter SP value of 9 (cal / cm ³ ). The polymer is ^1/2 or more.
The method for calculating the solubility parameter is described in R.A. F. Fedors, Polym. Eng. Sci. , 14, 147 (1974).

Specifically, it refers to the polymers listed below. Poly (meth) acrylic resin, polyether resin, polyester resin, polyurethane resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, polyamide resin, polycarbonate resin, epoxy resin, melamine resin, alkyd resin are used.
The poly (meth) acrylic resin used in the present invention is usually obtained by polymerizing an unsaturated carboxylic acid or its ester or anhydride by radical polymerization, anionic polymerization, or cationic polymerization. The bonding method with polyolefin (IIA) is not limited. For example, radical polymerization in the presence of polyolefin, poly (meth) having reactive groups such as hydroxyl group, amino group, glycidyl group and (anhydrous) carboxylic acid group. And a method of reacting an acrylic resin with a polyolefin polymer having a reactive group.

Examples of the monomer for forming the poly (meth) acrylic resin include (meth) acrylic acid ester monomers having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and carbonization having 1 to 12 carbon atoms. Examples thereof include a polymerizable vinyl monomer having a hydrogen group and a hydrophilic monomer having 1 to 12 carbon atoms.
Examples of the (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate.

Examples of the (meth) acrylic acid ester monomer having an aryl group or arylalkyl group having 1 to 12 carbon atoms include phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, and the like. It is done.
Examples of the polymerizable vinyl monomer having a hydrocarbon group having 1 to 12 carbon atoms include vinyl acetate and styrene monomer.

  Examples of the hydrophilic monomer having 1 to 12 carbon atoms include (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate (dimethyl) dimethylamine ethyl (meth) acrylate, (meth) Examples include acrylamide. Preferably, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate are used.

  Alternatively, a radically polymerizable unsaturated compound may be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to polyolefin (IIA), and then modified with polar polymer (IIB). Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. In this case, as the polyolefin (IIA), a polyolefin (IIA2) formed by bonding a reactive group can be used, but usually a polyolefin (IIA) having no reactive group is used.

The polyvinyl alcohol resin is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.
The polyvinyl pyrrolidone resin is usually obtained by polymerizing vinyl pyrrolidone.
The polyester resin can be usually obtained by condensation polymerization of diol and dicarboxylic acid or ring-opening polymerization of lactone. The modified olefin polymer is a method of ring-opening polymerization of a lactone by condensation polymerization in the presence of an olefin polymer having a reactive group, a method of condensation polymerization of a polyhydric alcohol and a polybasic acid, or a polyester resin having a reactive group. Can be obtained by a polymer reaction method.

The polyurethane resin is generally obtained by condensation polymerization of an organic diisocyanate, a polyol and a chain extender. The modified olefin polymer is obtained by a method of condensation polymerization with an organic diisocyanate, a polyol and a chain extender in the presence of an olefin polymer having a reactive group, or a method of polymerizing with a polyurethane resin having a reactive group. Can do.
The polyamide resin can be obtained, for example, by ring-opening polymerization of lactam or diamine and dicarboxylic acid. The modified olefin polymer is a method of ring-opening polymerization of a lactam in an olefin polymer having a reactive group, a method of condensation polymerization of a diamine and a dicarboxylic acid, a polyamide having a reactive group and an olefin having a reactive group. It can be produced by a method of reacting with a polymer.

  The polycarbonate resin can be usually obtained by a transesterification reaction between bisphenol and a dialkyl or diaryl ester. The modified olefin polymer is a method of reacting bisphenol with a dialkyl or diaryl ester in the presence of an olefin polymer having a reactive group, and reacting a polycarbonate resin having a reactive group with an olefin polymer having a reactive group. It can manufacture by the method to do.

In general, the epoxy resin can be obtained by a reaction between a phenol derivative and epichlorohydrin in the presence of a base. The modified olefin polymer is produced by a method of reacting a phenol derivative and epichlorohydrin in the presence of an olefin polymer having a reactive group, a method of reacting an epoxy resin and an olefin polymer having a reactive group, etc. Can do.
A melamine resin can be obtained by reaction of melamine and formaldehyde, for example. The modified olefin polymer is a method of reacting melamine and formaldehyde in the presence of an olefin polymer having a reactive group, a method of reacting a melamine resin having a reactive group and an olefin polymer having a reactive group, etc. Can be manufactured.

The alkyd resin can generally be obtained by a reaction between a polyhydric alcohol and a polybasic acid. The modified olefin polymer includes a method of reacting a polyhydric alcohol and a polybasic acid in the presence of an olefin polymer having a reactive group, an alkyd resin having a reactive group, and an olefin polymer having a reactive group. It can be produced by a reaction method or the like.
The polyether resin is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with polyolefin (IIA) is not limited, but, for example, polyether polyol obtained by ring-opening polymerization of cyclic alkylene oxide in copolymer (IIA2) having a reactive group, ring-opening polymerization, etc. And a method of reacting a polar polymer having a reactive group such as polyetheramine with a copolymer (IIA2) having a reactive group.

Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.
Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.

Or as a polyetheramine, you may use Huntsman's Jeffamine M series, D series, ED series, etc.
The polar polymer (IIB) used in the present invention preferably has at least one reactive group capable of reacting with the polyolefin (IIA) before bonding with the polyolefin (IIA). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and preferably have at least an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, a glycidyl group, and an isocyanate group, it is easy to bond a polyolefin and a polar polymer. The amino group may be primary, secondary, or tertiary, but is preferably a primary amino group.

The number of reactive groups may be one or more, but more preferably it has only one reactive group. When there are two or more reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with polyolefin (IIA), resulting in gelation.
However, even if it has a plurality of reactive groups, it is sufficient if only one reactive group is more reactive than the others. For example, a polar polymer having a plurality of hydroxyl groups and one amino group having a higher reactivity is a preferred example. Here, the reactivity is the reactivity with the reactive group of the polyolefin (IIA).

  The polar polymer (IIB) in the present invention needs to be a polymer in order to impart sufficient polarity to the polymer (IIC), and has a weight average molecular weight Mw measured by GPC and converted by a polystyrene calibration curve. 200 or more. The lower limit is preferably 300, more preferably 500. However, the weight average molecular weight Mw is preferably 200,000 or less. A more preferable value of the upper limit value is 100,000, and more preferably 10,000. As the Mw is higher than the lower limit, the polarity of the polymer (IIC) increases and the dispersed particle size tends to be smaller and stably dispersed. The lower the upper limit, the lower the viscosity and the easier it is to prepare a resin dispersion. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using THF or the like as a solvent.

  The amount of the polar polymer (IIB) bonded to the polyolefin (IIA) is preferably in the range of 0.01 to 5 mmol, ie 0.01 to 5 mmol / g, per 1 g of the polyolefin (IIA). A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. The upper limit value is more preferably 1 mmol / g, further preferably 0.8 mmol / g, particularly preferably 0.5 mmol / g, and most preferably 0.3 mmol / g. The higher the lower limit value, the greater the polarity of the polymer (IIC) and the smaller the dispersed particle size tends to be stably dispersed, and the lower the upper limit value, the greater the adhesion to the crystalline polyolefin as the substrate. .

  Polyolefin (IIA) and polar polymer (IIB) are a graft copolymer obtained by grafting polar polymer (IIB) to polyolefin (IIA), and polar polymer (IIB) at one or both ends of polyolefin (IIA). ) May be a block copolymer of polyolefin (IIA) and polar polymer (IIB) including a bonded state, and a graft copolymer is preferable. There are advantages that the content of the polar polymer (IIB) can be easily controlled and that the content of the polar polymer (IIB) can be easily increased as compared with the block copolymer.

The polar polymer (IIB) can be bonded to the polyolefin (IIA) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.
The reaction using a reactive group has a reactive group in both the polyolefin (IIA) and the polar polymer (IIB) and causes them to react and bond, and a covalent bond or an ionic bond is formed. The Examples of this reaction include esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted with respect to one equivalent of the dibasic acid or anhydride.

[3-3] Production Method of Polymer (IIC2) As a method of producing polymer (IIC) by combining polyolefin (IIA) and polar polymer (IIB), hydrophilic radical polymerization is usually performed in the presence of polyolefin. There is a method (R1) for polymerizing a polymerizable unsaturated compound to form a polar polymer (IIB) bonded to a polyolefin, or a method (R2) for bonding a previously polymerized polar polymer (IIB) to a polyolefin.

[3-3-1] Production method (R1) of polymer (IIC2)
In this method, a polar polymer (IIB) bonded to polyolefin is obtained by polymerizing a polar radical polymerizable unsaturated compound (polar monomer) in the presence of polyolefin. As a polymerization method of the polar radically polymerizable unsaturated compound, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic radical-polymerizable unsaturated compound may be copolymerized as long as a polar polymer can be formed after polymerization. In either case, polyolefin (IIA) having no reactive group or polyolefin (IIA2) formed by bonding a reactive group can be used as the polyolefin.

  Specifically, for example, there is a method in which a hydrophilic radical-polymerizable unsaturated compound is graft-polymerized into a polyolefin-polyacrylic graft copolymer in the presence of a polyolefin (IIA) and a radical polymerization initiator such as a peroxide or an azo compound. is there. Further, as described in JP-A No. 2001-288372, a hydrophilic radical-polymerizable unsaturated compound is prepared in the presence of polyolefin (IIA2c1) having a group 13 element group such as a boron group and an aluminum group at the terminal and oxygen. There is a method of polymerizing into a block copolymer of polyolefin and polyacryl. Furthermore, as described in JP-A-2004-131620 and JP-A-2005-48172, a polyolefin having a halogen atom at its terminal (IIA2c2), copper halide, ruthenium halide, etc. are used, and an atom transfer living radical method is used. There is a method of using a block copolymer of a propylene polymer and polyacryl. Further, as described in JP-A No. 2001-98140, a polyolefin / polyacryl block copolymer is obtained by polymerizing a radical initiator and a hydrophilic radical-polymerizable unsaturated compound in the presence of a polyolefin having a mercapto group at its terminal. There is a method.

Although it does not specifically limit as a polar radically polymerizable unsaturated compound, The monomer quoted as a monomer which forms the said poly (meth) acrylic resin can be used.
Reactive surfactants and reactive emulsifiers can also be used as the aqueous radical polymerizable unsaturated compound. Examples thereof include alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts and salts of sulfates thereof described in JP-A-4-53802 and JP-A-4-50204. Among them, alkyl propenyl phenol ethylene oxide 20 mol adduct, 30 mol adduct, 50 mol adduct (Daiichi Kogyo Seiyaku, Aqualon RN-20, RN-30, RN-50) and alkyl propenyl phenol polyethylene oxide 10 mol. Adduct sulfate ammonium salt and 20 mol adduct sulfate ammonium salt (Daiichi Kogyo Seiyaku, Aqualon HS-10, HS-20) are used.

Alternatively, a radically polymerizable unsaturated compound can be polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to polyolefin (IIA), and then the polar polymer (IIB) can be modified.
Alternatively, there is a method in which a polar polymer (IIB) is obtained by polymerizing a polar ring-opening polymerization monomer or the like using a polyolefin (IIA2) having a reactive group and using the reactive group as an initiation terminal.

Examples of the polar ring-opening polymerization monomer include ethylene oxide, propylene oxide, ethyleneimine, trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.
Any of these may be used alone or in combination of two or more.

  The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [3-1] can be used similarly.

[3-3-2] Production method (R2) of polymer (IIC2)
In this method, a prepolymerized polar polymer (IIB) is bonded to polyolefin (IIA). In this case, as the polar polymer (IIB), those mentioned in [3-2] can be used.
Specifically, for example, when a polar monomer is first polymerized into a polar polymer, an unsaturated double bond is left in the molecule, and then a method of graft polymerization to a polyolefin using a radical polymerizable initiator is used. is there. In this case, polyolefin (IIA2) having a reactive group can be used as the polyolefin, but polyolefin (IIA) having no reactive group is usually used.

  There is also a method in which a polar polymer having a reactive group at the terminal is first polymerized, and then this is bonded to a polyolefin (IIA2) formed by bonding a reactive group. A polar polymer having a reactive group at the terminal can be obtained by polymerizing a hydrophilic monomer using a compound having a reactive group as an initiator or a chain transfer agent. Alternatively, it can also be obtained by ring-opening polymerization of a hydrophilic ring-opening polymerization monomer such as an epoxy compound.

As polar monomers that can be used at this time, various polar monomers listed in [3-3-1] can be used in the same manner.
Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [3-1] can be used similarly.

[4] Manufacturing method of aqueous dispersion and non-aqueous dispersion of polymer (IIC) [4-1] Manufacturing method of aqueous dispersion The manufacturing method of the aqueous dispersion containing the polymer (IIC) according to the present invention is as follows. Although not particularly limited, for example, after preparing a mixture of the polymer (IIC), water, and a solvent other than water, and removing the solvent from the mixture, the polymer (IIC) is an aqueous dispersion. Examples of the method include a method in which water is added after melting at a melting temperature or higher to form a dispersion. The former is preferred. According to the former method, it is easy to obtain an aqueous dispersion having a fine particle size.

When preparing a mixture, you may heat as needed. The temperature is usually 30 to 150 ° C. The ratio of the solvent other than water in the aqueous dispersion is finally usually 50% or less. It is preferably 20% or less, more preferably 10% or less, and particularly preferably 1% or less.
Of these, a method of adding a solvent other than water to the polymer (IIC) and adding water after heating and dissolving as necessary is more preferable because an aqueous dispersion having a finer particle size can be easily produced. The temperature at the time of dissolution in a solvent or at the time of addition of water is usually 30 to 150 ° C. Moreover, when dissolving once in solvents other than water, after adding water, you may distill a solvent off. The ratio of the solvent other than water in the resin dispersion is as described above.

Alternatively, water having a small particle diameter can also be obtained by adding water and another solvent other than water to a solution in which the polymer (IIC) is dissolved in a solvent, heating and dissolving the solution as necessary, and then distilling off the solvent. Easy to make dispersion. The temperature at the time of addition of water is usually 30 to 150 ° C. The ratio of the solvent other than water in the resin dispersion is as described above.
Examples of the solvent other than water used in the present method include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic systems such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrocarbons, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol and other alcohols, dipropyl alcohol Organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, etc. , Polar solvents such as dimethylformamide and dimethyl sulfoxide.

  Among them, a solvent that dissolves 1% by mass or more in water is preferable, and more preferably 5% by mass or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol , Isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.

  An apparatus for producing a resin dispersion by adding water after the solvent is dissolved and melted is not particularly limited. For example, a reaction kettle with a stirring device, a uniaxial or biaxial kneader can be used. The stirring speed at that time varies slightly depending on the selection of the apparatus, but is usually in the range of 10 to 1000 rpm.

[4-2] Method for Producing Non-Aqueous Dispersion The method for producing the non-aqueous dispersion containing the polymer (IIC) according to the present invention is not particularly limited. A method of once dissolving in a polar solvent containing one or more heteroatoms and then precipitating and dispersing them, or adding a polar solvent containing one or more heteroatoms in the molecule after dissolving in a good solvent other than a polar solvent such as an aromatic solvent For example, a method of precipitating and dispersing, and distilling off the good solvent as necessary may be mentioned.

The temperature at the time of dissolution in a polar solvent or a good solvent or the addition of a polar solvent containing one or more heteroatoms in the molecule is usually 30 to 150 ° C. Further, the good solvent may be distilled off after adding the polar solvent.
Examples of the polar solvent used in the present method include those containing one or more heteroatoms in the molecule, for example, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, Ketones such as methyl isobutyl ketone and cyclohexanone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol and butanediol , Ethers such as dipropyl ether, dibutyl ether, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropa Lumpur, organic solvents having two or more functional groups such as diacetone alcohol, dimethyl formamide, a solvent such as dimethyl sulfoxide and the like.
Examples of the good solvent other than the polar solvent used in this method include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatics such as cyclohexane and methylcyclohexane. Based hydrocarbons.

[5] Aqueous dispersion and non-aqueous dispersion The dispersed particle diameter of the polymer (resin) in the aqueous dispersion and non-aqueous dispersion is 50% cumulative (50% When the particle diameter or 50% average particle diameter is determined, the 50% particle diameter is usually 10 μm or less, preferably 1 μm or less. According to the present invention, the 50% particle size can be 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the 90% particle diameter is determined, the 90% particle diameter can be more preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. Further, a reduction in the ratio of the 90% particle diameter to the 50% particle diameter means that the particle size distribution becomes narrow, and as a result, the dispersion stability is improved.

In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved. Accordingly, there is no particular limitation on the lower limit value of the dispersed particle size.
The solid content of the resin dispersion of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. Moreover, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The smaller the amount of solid content, the lower the viscosity, the easier it can be applied to various application methods and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

  In the resin dispersion of the present invention, a water-soluble resin or a resin that can be dispersed in water or a polar solvent can be mixed and used as necessary, as long as the effects of the present invention are not significantly impaired. For example, improvement in adhesion to the base film and various physical properties, specifically improvement in the appearance of coating (glossing or matting) and reduction in tackiness, coating strength, water resistance, weather resistance, abrasion resistance It is possible to improve the properties and solvent resistance. For example, the resins listed as polar polymer (IIB) can be used.

  Examples of the resin that can be dispersed in water or a polar solvent include acrylic resin, polyepoxy resin, polyester resin, polyurethane resin, melamine resin, alkyd resin, and the like. The form of the resin dispersion containing these resins and polymer (IIC) is not particularly limited. For example, there is a method of emulsifying and mixing these resins and the polymer (IIC). In this method, a resin dispersion in which particles made of these resins and particles made of the polymer (IIC) are separately formed and dispersed is obtained.

  The resin content is preferably in the range of 90:10 to 10:90 in mass ratio of polyolefin (IIA) to the other resin. That is, the total amount of polyolefin (IIA) and other resins is 100 parts by mass, and the amount of polyolefin (IIA) is preferably 10 parts by mass or more, more preferably 90 parts by mass or less. When the amount of the polyolefin (IIA) is less than 10 parts by mass, the adhesion to the polyolefin-based molded product tends to be insufficient. More preferably, it is 15 mass parts or more, More preferably, it is 20 mass parts or more. When the amount of polyolefin (IIA) is greater than 90 parts by mass, the physical properties of the coating obtained from such a composite aqueous resin dispersion, specifically, the strength, water resistance, weather resistance, abrasion resistance, Solvent property tends to be insufficient. More preferably, it is 85 mass parts or less, More preferably, it is 80 mass parts or less.

As said other resin, at least 1 or more resin chosen from the group which consists of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin is preferable. For example, those mentioned in [3-2].
The resin dispersion of the present invention usually has a surfactant content of 15 parts by mass or less with respect to 100 parts by mass of the polymer (IIC). That is, the dispersed particle diameter of the resin is very small and the surfactant is very little or substantially free of surfactant. Conventionally, particularly in the case of an aqueous dispersion, there has been a problem that a dispersion having a fine dispersed particle size cannot be obtained unless a large amount of surfactant is used. However, the polymer (IIC) of the present invention has a dispersibility as described above. Therefore, it is not necessary to use a large amount of surfactant. Thereby, when this resin dispersion is used as a coating material, there is an advantage that a bleed-out can be suppressed and a coated product having an excellent appearance can be obtained, and this resin dispersion can be used as a coating material on the outermost surface of coating. In addition, the water resistance and oil resistance (GH resistance) of the coating can be improved, and the resulting resin dispersion has any of adhesion, water resistance, moisture resistance, oil resistance (GH resistance), and chemical resistance. Will also be excellent.

  The amount of the surfactant is preferably small, and the surfactant content of the resin dispersion is preferably 10 parts by mass or less with respect to 100 parts by mass of the polymer (IIC). More preferably, it is 5 mass parts or less, More preferably, it is 2 mass parts or less. It can also be substantially free of surfactant. “Substantially free of surfactant” means less than 1 part by mass with respect to 100 parts by mass of the polymer (IIC).

  As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. As the surfactant, those having an alkyl group, alkenyl group, alkylaryl group or alkenylaryl group having 4 or more carbon atoms as a hydrophobic group are usually used. Preferably it is C8 or more, More preferably, it is C12 or more. However, it usually has 30 or less carbon atoms.

  Examples of the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate, and the like. Examples of the cationic surfactant include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and the like. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.

Moreover, what is called a reactive surfactant etc. in which said surfactant has a radically polymerizable functional group can also be used. When a reactive surfactant is used, the water resistance of a film formed using this resin dispersion can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).
In addition, since nonionic surfactant is hard to reduce water resistance compared with other surfactant, nonionic surfactant may be included a little more. For example, when the surfactant other than the nonionic surfactant should be 5 parts by mass or less with respect to 100 parts by mass of the polymer (IIC), the nonionic surfactant may be 10 parts by mass or less.

Further, according to the present invention, there is an advantage that it is not necessary to use a chlorinated polyolefin and the environmental load can be reduced.
An acidic substance or a basic substance can be added to the resin dispersion of the present invention as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of basic substances include inorganic bases such as sodium hydroxide and potassium hydroxide, triethylamine, diethylamine, diethylethanolamine, and 2-methyl-2-amino-propanol.

  The resin dispersion of the present invention can contain various additives as required within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors; colorants such as titanium oxide and organic pigments; conductivity imparting agents such as pigments, carbon black and ferrite, dyes, pigment dispersions Various additives such as additives, leveling agents, antifoaming agents, thickeners, preservatives, fungicides, rust inhibitors and wetting agents may be used in combination.

Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
In order to further improve various coating performances such as water resistance and solvent resistance. The crosslinking agent can be added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin in the dispersion. As the crosslinking agent, there can be used a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, etc. Among them, an isocyanate compound, Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

[5] Decorative sheet (III)
The decorative sheet (III) according to the present invention includes a base film (III-1), a design layer (III-2) for applying design properties, and an adhesive layer as its basic configuration.
[5-1] Substrate film (III-1)
The material of the base film (III-1) is not particularly limited as long as the pattern layer and the adhesive layer can be in close contact with each other. For example, acrylic resin, polyvinyl chloride resin, polypropylene resin, polyethylene resin, polyamide resin Thermosetting resins such as polyester resins, cured products of thermosetting resins such as polyurethane resins, and cured products of radiation curable resins such as polyester acrylates, epoxy acrylates, and urethane acrylates can be used.

Of these, radiation curable resins (cured products of radiation curable resins) are preferred because of excellent surface properties such as chemical resistance and contamination resistance. In particular, in applications where followability at the time of molding is required, a base film made of a urethane acrylate radiation curable resin having a crosslinked structure and having flexible coating film properties is preferable.
The base film made of urethane acrylate is usually (a-1) at least one polymer glycol selected from (a-1) organic diisocyanate, (a-2) polyether glycol, polyester glycol, and polycarbonate glycol, (a-3) It can be obtained by reacting a hydroxyalkyl (meth) acrylate and, if necessary, (a-4) a short-chain glycol having 2 to 12 carbon atoms.

(A-1) Organic diisocyanate (a-1) Examples of the organic diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and isophorone diisocyanate. (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H12MDI), alicyclic diisocyanates such as ω, ω′-diisocyanatodimethylcyclohexane, aliphatics having an aromatic ring such as xylylene diisocyanate, tetramethylxylylene diisocyanate Diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI) , Naphthalene-1,5-diisocyanate, aromatic diisocyanate and mixtures of two or more of these such as tolidine diisocyanate. Of these, IPDI and H12MDI are preferable for applications requiring weather resistance, and TDI and MDI are preferable for applications where mechanical strength is required.

(A-2) Polymer glycol (a-2) Examples of the polymer glycol include polyether glycol, polyester glycol, polyether ester glycol, and polycarbonate glycol. Examples of the polyether glycol include those obtained by ring-opening polymerization of a cyclic ether, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or anhydrides thereof and low molecular weight diols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptane, 1,9- Nonanediol, 2-methyl-1,8- Of lactones to low molecular weight diols such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene sebacate, etc. Examples thereof include those obtained by ring-opening polymerization such as polycaprolactone and polymethylvalerolactone.

Examples of the polyether ester glycol include those obtained by ring-opening polymerization of a cyclic ether to polyester glycol, those obtained by polycondensation of polyether glycol and dicarboxylic acid, such as poly (polytetramethylene ether) adipate.
Polycarbonate glycol includes polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc. obtained by deglycolization or dealcoholization from low molecular weight diol and alkylene carbonate or dialkyl carbonate, and co-polymers thereof. A polymer is mentioned.

Of these, polycarbonate glycol is preferred for applications requiring weather resistance.
Furthermore, polyolefin polyol, silicon polyol, etc. can be used in combination with the above-mentioned polymer glycol within a range that does not affect the effect of the present invention. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. Examples of the silicon polyol include polydimethylsiloxane polyol. The molecular weight of the polymer glycol has a lower limit of usually 200 or more, preferably 500 or more, and an upper limit of usually 10,000 or less, preferably 4000 or less, more preferably 2000 or less. If the molecular weight is too small, the obtained active energy ray-curable resin sheet is poor in flexibility, and if it is too large, the viscosity of the urethane (meth) acrylate oligomer tends to increase remarkably and the workability tends to decrease.

(A-3) Hydroxyalkyl (meth) acrylate (a-3) Hydroxyalkyl (meth) acrylate has radical reactivity by reacting an isocyanate group derived from (a-1) organic diisocyanate at the molecular end. Has the effect of imparting. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate. , 2-hydroxyethyl (meth) acrylate and caprolactone adduct, 4-hydroxybutyl (meth) acrylate and caprolactone adduct, and these can be used singly or in combination of two or more. . Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.

(A-4) Short chain glycol having 2 to 12 carbon atoms (a-4) Short chain glycol having 2 to 12 carbon atoms is not essential and is used as necessary. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1, 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3- Aliphatic diols such as pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, alicyclic diols such as cyclohexanedimethanol, bishydroxyethoxybenzene, bis Hydroxyethyl terephthalate, bis Phenol aromatic diols such as -A, such as dialkanolamines such as N- methyldiethanolamine, and mixtures of two or more thereof. In addition, polyols such as trimethylolpropane and glycerin can be used in combination within a range that does not hinder the effects of the present invention.

  As a method for producing a urethane (meth) acrylate oligomer, (1) an organic diisocyanate (a-1), a polymer glycol (a-2), and, if necessary, a short-chain glycol (a-4) in excess of NCO A prepolymer method in which an isocyanate-terminated urethane prepolymer reacted under the above conditions and a hydroxyalkyl (meth) acrylate (a-3) are reacted; (2) one shot in which all components are added simultaneously and reacted. (3) Urethane (meth) having an organic diisocyanate (a-1) and a hydroxyalkyl (meth) acrylate (a-3) previously reacted and having a (meth) acryloyl group and an isocyanate group in the molecule at the same time After synthesizing the acrylate prepolymer, the polymer glycol (a-2) and, if necessary, the short chain glycol How to respond, and the like.

  A base film may be formed in advance, and a pattern layer and an adhesive layer may be formed thereon, or an adhesive layer, a pattern layer, and a base film are sequentially formed on a carrier film that is another base material. May be peeled off.

[5-2] Pattern layer (III-2)
The pattern layer (III-2) can be formed using various known inks and is not particularly limited. For example, gravure printing, flexographic printing, silk screen printing, dry offset printing on the base film (III-1) using printing ink using acrylic resin, urethane resin, polyester resin, polyolefin resin, etc. It can be printed and formed by a printing method such as pad printing. The order of lamination is not particularly limited, and it can be printed on a base film as described above, or a picture layer is first laminated on a carrier film which is another base, and then for the base film. The base film may be formed by laminating the resin using a known printing method or coating method such as a gravure printing method, a roll coating method, or a comma coating method, followed by drying and curing. Alternatively, when the base film is a thermoplastic resin, it can be laminated by a lamination method such as extrusion lamination or coextrusion lamination.

[5-3] Method for producing decorative sheet The method for producing the decorative sheet of the present invention is not particularly limited, and a known method for producing a decorative sheet can be applied.
As a preferable example, after forming a pattern layer on a base film, an aqueous dispersion or a non-aqueous dispersion of a modified polyolefin is applied and dried to form an adhesive layer. As a coating method, a known printing or coating method such as a gravure printing method, a roll coating method, or a comma coating method can be used.
As another preferred example, an aqueous dispersion or non-aqueous dispersion of a modified polyolefin is coated on another substrate and dried to form an adhesive layer, then a pattern layer is formed, and a radiation curable resin is applied. After curing to form a substrate film, the other substrate is peeled off. The above-described coating method is also used in this case.

The thickness of the adhesive layer made of the modified polyolefin (II) is preferably 2 μm or more after drying, and more preferably 5 μm or more. It is for obtaining sufficient adhesiveness with a polyolefin-type molded object. However, it is preferably 50 μm or less, more preferably 30 μm or less. This is because coating is easy and the process can be simplified.
In order to enhance the effect of the present invention, modified polyolefin (II) may be separately applied to the surface of the molded body before the decorative sheet is bonded to the polyolefin-based molded body. As the application method, conventionally known methods such as a method of applying with a spray, a method of applying with a roller, and a method of applying with a brush can be used. Application to the molded body is preferably carried out at room temperature, and after the coating is applied, the coating is cured according to the usual method of heating with heating wire, infrared rays, high frequency, etc., and the molded body having the desired coating on the surface Can be obtained. The method for curing the coating film is appropriately selected depending on the material and shape of the molded body, the properties of the paint used, and the like. In order to obtain good adhesion, it is preferable to heat after application. Although there is no restriction | limiting in particular in heating temperature, Considering practicality, it is preferable to set it as 50-150 degreeC, Furthermore, it is 60-130 degreeC.

[6] Laminate [6-1] Polyolefin-based molded product (I)
The polyolefin-based molded article (I) used in the present invention is a molded article of crystalline polyolefin, and is a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene- 1, random copolymers or block copolymers with 2 or more, preferably 2-6 α-olefin comonomers such as heptene-1, octene-1, cyclopentene, cyclohexene, norbornene, or two or more of these comonomers Or a copolymer with a comonomer such as vinyl acetate or (meth) acrylate, an aromatic vinyl monomer / conjugated diene block copolymer, or a hydrogenated product thereof. These can be used alone or as a mixture depending on the application.

  More preferred as the polyolefin is crystalline polypropylene. Crystalline polypropylene is a propylene homopolymer and / or a propylene / ethylene copolymer. Here, the propylene / ethylene copolymer is a propylene / ethylene random copolymer and / or a propylene / ethylene block copolymer, and preferably a propylene / ethylene block copolymer.

  The polyolefin preferably has a melt flow rate (MFR) of 2 g / 10 min or more, more preferably 10 g / 10 min or more, and particularly preferably 25 g / 10 min. However, it is preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less. If the MFR is higher than the lower limit, the flowability of the polyolefin tends to increase. Conversely, if the MFR is lower than the upper limit value, the mechanical properties tend to increase. The MFR of the polyolefin may be adjusted at the time of polymerization, or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after the polymerization.

<Inorganic filler component>
The polyolefin-based molded product (I) used in the present invention can contain an inorganic filler component.
In particular, by blending an inorganic filler component with crystalline polyolefin, mechanical properties such as flexural modulus and rigidity of the molded product can be improved.
Specifically, plate fillers such as talc, mica and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber and zonolite; potassium titanate, magnesium Needle-like fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Granular fillers; balun fillers such as glass balloons; Inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate can also be used. Of these, talc, mica, glass fiber, and whisker are preferable from the balance between physical properties and cost, and talc, mica, and glass fiber are more preferable.

The inorganic filler component may be surface-treated with a surfactant, a coupling agent or the like. The surface-treated filler has an effect of further improving the strength and heat-resistant rigidity of the molded product.
The amount of the inorganic filler component used is selected from a wide range depending on the purpose and application of the molded product, but is preferably 1 to 80 parts by mass, more preferably 2 to 75 parts by mass, and more preferably 100 parts by mass of the crystalline polyolefin. Preferably it is 5-60 mass parts.

By including the inorganic filler component, the flexural modulus of the crystalline polyolefin can be improved to preferably 1000 MPa or more, more preferably 1500 to 10000 MPa, and still more preferably 2000 to 8000 MPa. The IZOD impact strength can be improved to preferably 1 kJ / m ² or more, more preferably ^{2 to} 80 kJ / m ² , and further preferably 4 to 60 kJ / m ² .
An inorganic filler component may be used individually by 1 type, and may be used in combination of 2 or more type.

<Elastomer component>
When the polyolefin-based molded article (I) used in the present invention is a crystalline polyolefin molded article, an elastomer component can be further contained. Thereby, the impact strength of the molded product can be improved.
Examples of the elastomer component include ethylene-α-olefin random copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene-α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Polymer rubber; Ethylene-α-olefin-nonconjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM); Hydrogenated product of styrene-butadiene-styrene triblock (SEBS), styrene -A styrene-containing thermoplastic elastomer such as hydrogenated product (SEPS) of isoprene-styrene triblock body can be exemplified.

These elastomers can be produced as follows.
The MFR (230 ° C., 2.16 kg load) of these elastomer components is preferably 0.5 to 150 g / 10 min, more preferably 0.000 when considering the automobile exterior material which is one of the main uses of the present invention. It is 7-100 g / 10min, More preferably, it is 0.7-80g / 10min.
An elastomer component may be used individually by 1 type, and may be used in combination of 2 or more type.

<Other ingredients>
In addition to the above, the polyolefin-based molded article (I) can contain any additive or compounding component as long as the effects of the present invention are not significantly impaired. Specifically, pigments for coloring, antioxidants such as phenols, sulfurs and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, dispersion Agents, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, polyethylene resins, and the like.

[6-2] Manufacturing method of polyolefin-based molded body (I) In manufacturing the polyolefin-based molded body (I), various components are blended with the above-described resin as necessary, and mixed and melt-kneaded. The kneading method is not particularly limited, and the polyolefin of the present invention is obtained by kneading and granulating using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader. A polyolefin composition constituting the molded body (I) is obtained. In order to improve the dispersion of each component, a twin screw extruder is preferably used.

When kneading and granulating, the above components may be kneaded at the same time, or a method of kneading the components separately may be employed in order to improve performance.
Next, the thermoplastic resin composition is molded to obtain the polyolefin-based molded product (I), and various known methods can be used as the molding method.
Examples include injection molding (including gas injection molding), compression molding, injection compression molding (press injection), extrusion molding, hollow molding, rotational molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, and the like. It is done. Preferably, injection molding, compression molding, and injection compression molding are used, and injection molding is particularly preferable in consideration of productivity and the like.

[6-3] Method for Producing Laminate The method for obtaining the laminate of the present invention by laminating a decorative sheet on these polyolefin-based molded products (I) is not particularly limited. After obtaining the body, decorate by vacuum molding, pressure forming, vacuum / pressure forming, or decorate the decorative sheet by insert molding after forming a preform by vacuum forming and / or pressure forming Various methods such as a decoration method by a method, a transfer method or a simultaneous integral molding method may be mentioned.

Specifically, for example, molding techniques such as JP-B-56-45768, JP-B-60-58014, JP-B-50-19132, and JP-A-11-91041 are exemplified.
The laminated body (decorative molded body) of the present invention is used in various industrial parts fields, in particular, various molded articles that are thin, highly functional, and large in size, such as automobile parts such as bumpers, instrument panels, trims, garnishes, and televisions. Cases, washing machine tubs, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat covers, water tank and other toiletry parts, bathtubs, bathroom walls, ceiling parts, drain pans, etc. As a molding material for various industrial parts such as parts around the bathroom, it has sufficient performance for practical use.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.
<Measurement of physical properties>
(1) Stereoregularity The stereoregularity [mmmm] of polypropylene was measured by a ¹³ C-NMR spectrum measurement method using an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a flip angle of 90 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group. Therefore, under this measurement condition, the recovery of the magnetization of all the carbons is 99% or more. Measurement was carried out by integrating over 20 hours.

(2) Molecular weight First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by mass of BHT was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a PTFE (polytetrafluoroethylene) filter having a pore diameter of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by mass. Next, GPC measurement was performed by using TSKgel GM H-HT (30 cm × 4) as a column and Waters GPC150CV equipped with an RI detector. As measurement conditions, the injection amount of the sample solution: 500 μl, column temperature: 135 ° C., solvent: orthodichlorobenzene, flow rate: 1.0 ml / min were employed.

When calculating the molecular weight, use a commercially available monodisperse polystyrene as a standard sample, create a calibration curve for retention time and molecular weight from the polystyrene standard sample and the viscosity formula of polypropylene, and calculate the molecular weight of the propylene polymer. went.
[Η] K · Mα is used as the viscosity formula, K = 1.38E-4 and α = 0.70 for polystyrene, and K = 1.03E− for propylene-based copolymers. 4, α = 0.78 was used.

(3) Graft rate 200 mg of the polymer and 4800 mg of chloroform are put into a 10 ml sample bottle and heated at 50 ° C. for 30 minutes to be completely dissolved. Chloroform was placed in a liquid cell having a material NaCl and an optical path length of 0.5 mm as a background. Next, the dissolved polymer solution was placed in a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation at 32 times. The graft ratio of maleic anhydride was calculated using a calibration curve prepared by measuring a solution of maleic anhydride in chloroform. Then, from the area of the absorption peak of the carbonyl group (maximum peak in the vicinity of 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer is calculated based on a separately prepared calibration curve, and this is calculated as the graft ratio ( Mass%).

(4) Dispersion particle diameter It measured using Microtrac UPA (model 9340 batch type dynamic light scattering method / laser Doppler method) by Nikkiso Co., Ltd. Measured with a dispersion density of 0.9 g / cm ³ , a particle shape of a true sphere, a particle refractive index of 1.50, a dispersion medium of water and a dispersion medium of 1.33, and a measurement time of 120 seconds. In terms of volume, 50% particle diameter and 90% particle diameter were calculated from the smaller particle diameter.

(5) Heat-seal test The polyolefin molded sheet described in Production Example 1 was heat-tested by using a heat seal tester TP-701 manufactured by Tester Sangyo Co., Ltd., and the decorative sheet was pressed at a temperature of 100 ° C., a load of 1 kgf / cm ² for 1 minute. A test piece was prepared. The obtained test piece was allowed to stand at room temperature for 24 hours and then subjected to a 180 ° peel test using a FUDOH rheometer NRM-2003J.

[Production Example 1: Production of polar polymer-modified polypropylene aqueous dispersion]
(1-1) 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected in a 1,000 ml round bottom flask and dissolved under stirring. In this solution, 16.7 g of commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried overnight at 110 ° C. under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.

To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd.) was collected, 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- 1-Azulenyl) hafnium 131 mg (57 μmol) in toluene was added, and the mixture was stirred at room temperature for 10 minutes to obtain a catalyst slurry (see JP-A 2004-002310 for the method for producing the catalyst).

(1-2) Toluene (11 L), triisobutylaluminum (3.5 mmol) and liquid propylene (2.64 L) were introduced into an induction stirring autoclave having an internal volume of 24 liters. At room temperature, the entire amount of the catalyst slurry obtained in Production Example (1-1) was introduced, the temperature was raised to 67 ° C., the total pressure during polymerization was kept constant at 0.65 MPa, and stirring was continued for 2 hours at the same temperature. did. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed. As a result, 11 kg (1.2 kg propylene polymer) of a 10.9% by mass propylene polymer toluene solution was obtained. The obtained polypropylene had a molecular weight of Mw 191,000 and a stereoregularity [mmmm] of 45.8%.

(1-3) In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, toluene (650 g), polypropylene (350 g) obtained in Production Example (1-2), and the inside of the container were replaced with nitrogen gas. The temperature was raised to 110 ° C. After the temperature rise, maleic anhydride (14 g) was added, perbutyl I (t-butylperoxyisopropyl monocarbonate, manufactured by NOF Corporation) (4.7 g) was added, and the reaction was continued by stirring at the same temperature for 10 hours. . After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.25% by weight (0.125 mmol / g). As a result of GPC measurement, the weight average molecular weight was 120,000.

(1-4) 30 g of maleic anhydride-modified polypropylene (content of maleic anhydride group: 3.75 mmol) synthesized in Production Example (1-3) in a glass flask equipped with a reflux condenser, a thermometer and a stirrer and 60 g of toluene And the temperature was raised to 110 ° C. to completely dissolve. Huntsman's polyetheramine Jeffamine M-1000 (methoxypoly (oxyethylene / oxypropylene) -2-propylamine: molecular weight 1000) in a solution of 7.5 g (7.5 mmol) dissolved in 10 g of toluene was added at 110 ° C. Reacted for hours. After cooling, toluene was distilled off under reduced pressure to obtain 37 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride in the vicinity of 1784 cm −1 disappeared, and maleic anhydride-modified polypropylene and polyetheramine were completely bonded.

  75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. The temperature was cooled to 40 ° C., the pressure was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 25% by weight to obtain a pale yellow milky white aqueous dispersion.

As a result of measuring the dispersed particle size, the 50% average particle size was 0.05 μm.
[Production Example 2: Production of maleic anhydride-modified polypropylene solution]
(2-1) A catalyst slurry was obtained in the same manner as in Production Example (1-1).
(2-2) 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. At room temperature, all of the above catalyst slurry was introduced, the temperature was raised to 69 ° C., the total pressure during polymerization was kept constant at 0.65 MPa, 8000 ppm of hydrogen was introduced into the gauge system, and stirring was continued for 2 hours at the same temperature. did. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 11 kg (1.4 kg propylene polymer) of a 12.5% by mass propylene polymer toluene solution was obtained. The weight average molecular weight Mw of the obtained polypropylene was 56,000, and the stereoregularity [mmmm] was 40.6%.

(2-3) In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 500 g of toluene and 500 g of polypropylene obtained in Production Example (2-2) were placed, and the inside of the container was replaced with nitrogen gas. The temperature was raised to ° C. After raising the temperature, 10 g of maleic anhydride was added, 3.3 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued for 10 hours at the same temperature. After completion of the reaction, the reaction mixture was cooled to 100 ° C., and 1500 g of methylcyclohexane was added to obtain an acid-modified polypropylene solution (20% by mass concentration). As a result of measuring the infrared absorption spectrum of this modified polymer, the maleic anhydride group content (graft ratio) was 0.50 wt% (maleic anhydride group 0.050 mmol / g, reactive group 0.10 mmol). / G). As a result of GPC measurement, the weight average molecular weight was 48,000.

[Production Example 3: Production of radiation curable resin for decorative sheet base film]
A 4-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 113 parts by mass of isophorone diisocyanate, heated to 50 ° C., and heated with stirring to polycarbonate diol (Kuraray polyol C-1090, hydroxyl group) 112 KOHmg / g, 205 parts by mass (manufactured by Kuraray Co., Ltd.), 33 parts by mass of 1,9-nonanediol (manufactured by Kuraray Co., Ltd.) and 0.01 parts by mass of dibutyltin dioctoate were added dropwise over about 1 hour. After keeping the temperature at 80 ° C. and reacting for 4 hours, 26 parts by mass of hydroxyethyl acrylate, 0.22 parts by mass of methylhydroquinone and 0.07 parts by mass of dibutyltin dioctoate were added, and further reacted at 70 ° C. for 3 hours. The end point of the reaction was confirmed by disappearance of a peak derived from an isocyanate group in the vicinity of 2260 cm ⁻¹ by measurement of an infrared absorption spectrum. Then, 274 parts by mass of isobornyl acrylate and 34 parts by mass of N-vinylformamide ((A) / (B) = 55/45 weight ratio as a dilution monomer (B) to the obtained urethane (meth) acrylate oligomer (A) ) Was added dropwise to obtain a urethane (meth) acrylate oligomer blending liquid having a viscosity of 19600 mPa · s.

[Production Example 4: Production of polyolefin-based molded article]
Polypropylene-ethylene copolymer resin (melt flow rate measured at 230 ° C., load 21.18 N: 0.7 g / 10 min, “EG8” manufactured by Nippon Polychem Co., Ltd.) 60% by weight and ethylene-propylene-nonconjugated diene copolymer Using a injection molding machine (IS170, manufactured by Toshiba Machine Co., Ltd.), a molding temperature of 40% by weight of a combined rubber (ethylene content: 66%, diene content: 4.5%, JSR "EP57P") A test piece of 150 mm × 70 mm × 2 mm was injection-molded at a setting of 220 ° C. to obtain a molded body for paintability evaluation.

[Decoration sheet production example 1]
The polyolefin aqueous dispersion obtained in Production Example 1 was applied to a Teflon (registered trademark) sheet having a thickness of 200 μm using a bar coater so as to have a dry film thickness of 5 μm, and dried at 80 ° C. for 10 minutes. Furthermore, acrylic urethane printing ink was applied to a thickness of 5 μm as a single layer and dried at 60 ° C. for 20 minutes. Thereafter, the urethane (meth) acrylate oligomer mixture obtained in Production Example 3 was applied using an applicator to a thickness of about 100 μm, and using an electron beam irradiation device CB175 manufactured by Eye Graphics Co., Ltd., an oxygen concentration of 100 ppm or less. In the atmosphere, the electron beam was irradiated and cured under the conditions of an acceleration voltage of 175 KV and an irradiation dose of 5 Mrad, and the Teflon (registered trademark) sheet was peeled off to obtain a decorative sheet (1).

[Decoration sheet production example 2]
A 120 μm thick acrylic resin sheet (methyl methacrylate-butyl methacrylate copolymer, glass transition temperature 105 ° C.) is used as a base film, and acrylic urethane printing ink is applied in a single layer to a thickness of 5 μm. Dried for minutes. Thereafter, the aqueous polyolefin dispersion obtained in Production Example 1 was applied to a dry film thickness of 5 μm and dried at 60 ° C. for 20 minutes to obtain a decorative sheet (2).

[Decoration sheet production example 3]
A decorative sheet (3) was obtained in the same manner as in the decorative sheet production example 1 except that an adhesive layer was formed using the acid-modified polypropylene solution obtained in Production Example 2.

[Decoration sheet production example 4]
A decorative sheet (3) was prepared in the same manner as in the decorative sheet production example 1 except that an adhesive layer was formed using a xylene solution of acid-modified chlorinated polypropylene (CP343-1, 25% by mass, manufactured by Eastman Chemical). Obtained.

[Decoration sheet production example 5]
A decorative sheet (4) was obtained in the same manner as in the decorative sheet production example 2 except that an adhesive layer was formed using an acid-modified chlorinated polypropylene aqueous dispersion (CP349W, 20 mass% concentration, manufactured by Eastman Chemical). .

[Example 1]
The decorative sheet (1) is placed on the polyolefin-based molded body obtained in Production Example 4 so that the adhesive layer is in contact with the molded body, and is pressed under pressure at a temperature of 80 ° C. and a load of 1 kgf / cm ² for 1 minute. Thus, a laminate was produced. The obtained laminate is allowed to stand at room temperature for 24 hours, and then the decorative sheet and the adhesive layer are cut so as to be 1 cm wide, and the end of the 1 cm wide decorative sheet and the end of the polyolefin-based molded body Were sandwiched between adapters, and a 180 ° peel test was conducted.
The peel strength was 3000 g / cm or more, and the adhesion was sufficient.

[Comparative Example 1]
A laminate was produced in the same manner as in Example 1 except that the decorative sheet (3) was used, and a 180 ° peel test was conducted in the same manner.
The peel strength was 750 g / cm, and the adhesion was insufficient.

[Comparative Example 2]
A laminate was produced in the same manner as in Example 1 except that the decorative sheet (4) was used, and a 180 ° peel test was conducted in the same manner.
The peel strength was 60 g / cm, and the adhesion was insufficient.

[Comparative Example 3]
A laminate was prepared in the same manner as in Example 1 except that the decorative sheet (5) was used, and a 180 ° peel test was performed in the same manner.
The peel strength was 400 g / cm, and the adhesion was insufficient.
The evaluation results of Examples and Comparative Examples are summarized in Table 1.

Claims (6)

  A decorative sheet comprising a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, wherein the adhesive layer is formed by applying an aqueous dispersion or a non-aqueous dispersion of the modified polyolefin and drying. Decorative sheet characterized by.   The decoration according to claim 1, wherein the modified polyolefin is a block and / or graft copolymer of a polyolefin and a polar polymer, and the surfactant content is 15 parts by mass or less with respect to 100 parts by mass of the modified polyolefin. Sheet.   The decorative sheet according to claim 1 or 2, wherein the base film is made of a radiation curable resin.   The laminated body by which the decorating sheet of any one of Claims 1 thru | or 3 is laminated | stacked on a polyolefin-type molded object.   A method for producing a decorative sheet comprising a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, wherein after the pattern layer is formed on the base film, an aqueous dispersion or non-aqueous dispersion of the modified polyolefin is formed. The manufacturing method of the decorating sheet | seat characterized by forming an contact bonding layer by apply | coating and drying.   A method for producing a decorative sheet comprising a base film, an image layer, and an adhesive layer containing a modified polyolefin, wherein the aqueous dispersion or non-aqueous dispersion of the modified polyolefin is applied onto another base and dried to be bonded. A method for producing a decorative sheet, comprising: forming a pattern layer; forming a pattern layer; applying a radiation curable resin; and curing to form a base film; and then peeling the other base.